Harnessing Interfacial Electronic Effects to Advance Electrocatalytic Ammonia Synthesis

ABSTRACT With the imbalance of the global nitrogen cycle, electrocatalytic nitrate reduction reaction (NO 3 − RR) has gained prominence as an important green ammonia synthesis pathway. However, the challenge of achieving high selectivity and efficiency in electrocatalytic systems remains a major impediment to the fundamental understanding of reaction mechanisms and industrial applications. To address the above bottlenecks, interfacial electronic effects, which serve as a pivotal strategy to regulate the intrinsic activity of catalysts, provide a solution to optimize the spatial charge distribution of active sites and thermodynamic descriptors of intermediate binding, which, however, has drawn little attention in review articles. Therefore, this review first analyzes the theoretical basis and mechanisms of interfacial electronic effects in NO 3 − RR, encompassing charge transfer, d‐band center theory, and orbital hybridization. Then, methods for advanced catalyst design based on this strategy are reviewed, including heterogeneous structures, alloys, metal‐supported interactions, defect engineering and single‐atom catalysts. Their potential for enhancing the efficiency and scalability of ammonia production in industrial applications is discussed. Finally, emerging trends and innovative opportunities for enhancing the NO 3 − RR process through modulation of interfacial electronic effects are discussed. This review delineates the pivotal contributions of interfacial electronic effects in NO 3 − RR and provides a theoretical framework and technological path for the development of efficient nitrate reduction electrocatalysts.